Carbonyl-Assisted Iridium-Catalyzed C-H Amination Using 2,2,2-Trichloroethoxycarbonyl Azide

The carbonyl-directed, mono C-H amination of arenes has been achieved using [Cp*Ir(III)Cl₂]₂ as the catalyst and 2,2,2-trichloroethoxycarbonyl (Troc) azide as an aminating reagent. The amination proceeds smoothly with a variety of arylcarbonyl compounds, including alkyl and vinyl arylketones, secondary and tertiary aryl amides, and acetyl indoles. The resulting ortho-TrocNH arylcarbonyl compounds are easily transformed to the corresponding free arylamines, aryl carbamates, or aryl ureas. Taking advantage of the electrophilic nature of both Troc and carbonyl groups in ortho-TrocNH arylcarbonyl compounds, the subsequent cyclization with dinucleophilic reagents has also been demonstrated. This provides an efficient strategy for the construction of aryl-fused N-heterocycles.